Electrodeposition baths, systems and methods

ABSTRACT

Electrodeposition baths, systems and methods are provided. In some embodiments, the baths, systems and methods are used to deposit metal alloy coatings.

RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.12/267,010, filed Nov. 7, 2008, now U.S. Pat. No. 7,951,600 which isincorporated herein by reference in its entirety.

FIELD OF INVENTION

This invention relates generally to electrodeposition baths, systems andmethods. In some embodiments, the baths, systems and methods are used todeposit metal alloy coatings.

BACKGROUND OF INVENTION

Electrodeposition is a common technique for depositing material on asubstrate. Electrodeposition generally involves applying a voltage to asubstrate placed in an electrodeposition bath to reduce metal ionicspecies within the bath which deposit on the substrate in the form of ametal, or metal alloy, coating. The voltage may be applied between ananode and a cathode using a power supply. At least one of the anode orcathode may serve as the substrate to be coated. In someelectrodeposition processes, the voltage may be applied as a complexwaveform such as in pulse plating, alternating current plating, orreverse-pulse plating.

A variety of metal and metal alloy coatings may be deposited usingelectrodeposition. For example, metal alloy coatings can be based on twoor more transition metals. Tungsten-based coatings are one example of anelectrodeposited coating. Such coatings may be tungsten alloys includingone or more of the elements Ni, Fe, Co, B, S and P. These coatings oftenexhibit desirable properties, including high hardness, abrasionresistance, good luster, wear properties, coefficient of friction insliding applications, amongst others.

Generally, the electrodeposition baths include one or more metal sourcesas well as additives that may improve the deposition process and/or theresulting coating. The metal source(s) may be selected based on thedesired composition of the metallic coating on the article. Typicaladditives include wetting agent(s), brightening agent(s), levelingagent(s), carrier(s), ductility agent(s), and others.

There is ongoing need for developments of new additives and/or newadditive combinations to further improve the deposition process and/orthe resulting coating. In particular, there is a need for new additivesand/or new additive blends that are effective in electrodepositionprocesses that use complex waveforms such as in pulse plating,alternating current plating, or reverse-pulse plating.

SUMMARY OF INVENTION

Electrodeposition baths and methods are described.

In one aspect, an electrodeposition bath is provided. Theelectrodeposition bath comprises tungsten and/or molybdenum ionicspecies and ionic species of a second metal. The electrodeposition bathfurther comprises a brightening agent comprising an alkynyl alkoxyalkane compound.

In another aspect, an electrodeposition bath is provided. Theelectrodeposition bath comprises tungsten and/or molybdenum ionicspecies and ionic species of a second metal. The electrodeposition bathfurther comprises a wetting agent comprising a sulfopropylatedpolyalkoxy napthol compound.

In another aspect, an electrodeposition bath is provided. Theelectrodeposition bath comprises tungsten and/or molybdenum ionicspecies and ionic species of a second metal. The electrodeposition bathfurther comprises a wetting agent comprising an anionic, non-ionic, oramphoteric fluorocarbon compound.

In another aspect, a method for electrodepositing a tungsten- and/ormolybdenum-based coating is provided. The method comprises providing ananode, a cathode, an electrodeposition bath associated with the anodeand the cathode, and a power supply connected to the anode and thecathode, the electrodeposition bath comprising tungsten and/ormolybdenum ionic species, ionic species of a second metal and abrightening agent comprising an alkynyl alkoxy alkane compound. Themethod further comprises driving the power supply to generate a waveformto electrodeposit a coating on a substrate.

In another aspect, a method for electrodepositing a tungsten- and/ormolybdenum-based coating is provided. The method comprises providing ananode, a cathode, an electrodeposition bath associated with the anodeand the cathode, and a power supply connected to the anode and thecathode, the electrodeposition bath comprising tungsten and/ormolybdenum ionic species, ionic species of a second metal and a wettingagent comprising a sulfopropylated polyalkoxy napthol. The methodfurther comprises driving the power supply to generate a waveform toelectrodeposit a coating on a substrate.

In another aspect, a method for electrodepositing a tungsten- and/ormolybdenum-based coating is provided. The method comprises providing ananode, a cathode, an electrodeposition bath associated with the anodeand the cathode, and a power supply connected to the anode and thecathode, the electrodeposition bath comprising tungsten and/ormolybdenum ionic species, ionic species of a second metal and a wettingagent comprising an anionic, non-ionic, or amphoteric fluorocarboncompound. The method further comprises driving the power supply togenerate a waveform to electrodeposit a coating on a substrate.

In another aspect, a method for electrodepositing a tungsten- and/ormolybdenum-based coating is provided. The method comprises providing ananode, a cathode, an electrodeposition bath associated with the anodeand the cathode, and a power supply connected to the anode and thecathode, the electrodeposition bath comprising tungsten and/ormolybdenum ionic species, ionic species of a second metal and abrightening agent comprising an alkyne compound. The method furthercomprises driving the power supply to generate a waveform toelectrodeposit a coating on a substrate, the waveform comprising atleast one forward pulse and at least one reverse pulse.

In another aspect, a method of analyzing an alkynyl alkoxy alkanecompound in an electroplating bath is provided. The method comprisesremoving a sample from an electroplating bath comprising a tungstenand/or molybdenum ionic species, an ionic species of a second metal, anda brightening agent comprising an alkynyl alkoxy alkane compound andadding a metal compound to the sample to form a metal-bound species byreaction of the alkynyl alkoxy alkane compound with the metal compound.The method further comprises analyzing the metal-bound species.

In another aspect, a method for analyzing an alkyne compound in anelectroplating bath is provided. The method comprises removing a samplefrom an electroplating bath comprising a tungsten and/or molybdenumionic species, an ionic species of a second metal, a brightening agentcomprising an alkynyl alkoxy alkane compound, and a secondarybrightening agent comprising an alkyne compound. The method furthercomprises extracting the alkyne compound from the sample by addition ofan organic solvent to the sample, reacting the alkyne with an oxidizingagent to produce a reacted alkyne, and analyzing the reacted alkyne.

Other aspects, embodiments and features of the invention will becomeapparent from the following detailed description when considered inconjunction with the accompanying drawings. The accompanying figures areschematic and are not intended to be drawn to scale. For purposes ofclarity, not every component is labeled in every figure, nor is everycomponent of each embodiment of the invention shown where illustrationis not necessary to allow those of ordinary skill in the art tounderstand the invention. All patent applications and patentsincorporated herein by reference are incorporated by reference in theirentirety. In case of conflict, the present specification, includingdefinitions, will control.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows an electrodeposition system according to an embodiment.

FIG. 2 shows an example of a waveform comprising a reverse pulsesequence according to an embodiment.

FIG. 3 shows an example of a waveform comprising (i) a first segmentincluding a single, forward pulse and (ii) a second segment including areverse pulse sequence.

DETAILED DESCRIPTION

Electrodeposition baths and methods are described. The baths include oneor more additives that promote deposition of coatings that exhibitdesirable properties and characteristics which can include brightness,surface levelness, reflectivity, hardness and ductility. The coatings,for example, may comprise a tungsten alloy such as a nickel-tungstenalloy. In some cases, the coatings may comprise molybdenum instead of orin addition to tungsten. As described further below, the additives caninclude a brightening agent comprising an alkynyl alkoxy alkane compoundand/or a wetting agent comprising a sulfopropylated polyalkoxy naptholcompound. In some embodiments, a brightening agent comprising an alkynecompound is used. The additives have been found to be particularlyeffective when used in combination with an electrodeposition processthat utilizes a complex waveform such as reverse pulse.

FIG. 1 shows an electrodeposition system 10 according to an embodiment.System 10 includes a electrodeposition bath 12. As described furtherbelow, the bath includes the metal sources used to form the coating andone or more additives. An anode 14 and cathode 16 are provided in thebath. A power supply 18 is connected to the anode and the cathode.During use, the power supply generates a waveform which creates avoltage difference between the anode and cathode. The voltage differenceleads to reduction of metal ionic species in the bath which deposit inthe form of a coating on the cathode, in this embodiment, which alsofunctions as the substrate.

It should be understood that the illustrated system is not intended tobe limiting and may include a variety of modifications as known to thoseof skill in the art.

The electrodeposition baths comprise a fluid carrier for the metalsource(s) and additive(s). In some embodiments, the fluid carrier iswater. However, it should be understood that other fluid carriers mayalso be used such as molten salts, cryogenic solvents, alcohol baths,amongst others. Those of ordinary skill in the art are able to selectsuitable fluid carriers.

The pH of the electrodeposition bath can be from about 2.0 to 12.0. Insome cases, the electrodeposition bath may have a pH from about 7.0- to9.0, or, in some cases, from about 7.6 to 8.4, or, in some cases, fromabout 7.9 to 8.1. However, it should be understood that the pH may beoutside the above-noted ranges.

In some cases, the operating range for the electrodeposition bathsdescribed herein is 30-100° C., 40-90° C., 50-80° C., or, in some cases,50-70° C. However, it should be understood that other temperature rangesmay also be suitable.

The baths include suitable metal sources for depositing a coating withthe desired composition. When depositing a metal alloy, it should beunderstood that all of the metal constituents in the alloy have sourcesin the bath. The metal sources are generally ionic species that aredissolved in the fluid carrier. As described further below, during theelectrodeposition process, the ionic species are deposited in the formof a metal, or metal alloy, to form the coating. In general, anysuitable ionic species can be used. The ionic species may be metalsalts. For example, sodium tungstate, ammonium tungstate, tungstic acid,etc. may be used as the tungsten source when depositing a coatingcomprising tungsten; and, nickel sulfate, nickel hydroxy carbonate,nickel carbonate, nickel hydroxide, etc. may be used as the nickelsource to deposit a coating comprising tungsten. In some cases, theionic species may comprise molybdenum. It should be understood thatthese ionic species are provided as examples and that many other sourcesare possible.

As described herein, the electrodeposition baths may include one or morecomponents (e.g., additives) that may enhance the performance of thebaths in producing coated articles.

In some embodiments, the baths may include at least one brighteningagent. The brightening agent may be any species that, when included inthe baths described herein, improves the brightness and/or smoothness ofthe metal coating produced. In some cases, the brightening agent is aneutral species. In some cases, the brightening agent comprises acharged species (e.g., a positively charged ion, a negatively chargedion). In one set of embodiments, the brightening agent may comprise analkyl group, optionally substituted. In some embodiments, thebrightening agent may comprise a heteroalkyl group, optionallysubstituted.

In some cases, the brightening agent may be an alkynyl alkoxy alkane.For example, the brightening agent may comprise a compound having thefollowing formula,H—C≡C—[CH₂]_(n)—O—[R¹],wherein n is an integer between 1 and 100, and R′ is alkyl orheteroalkyl, optionally substituted. In some cases, the R¹ is an alkylgroup, optionally substituted with OH or SO₃. In some embodiments, R¹comprises a group having the formula (R²)_(m), wherein R² is alkyl orheteroalkyl, optionally substituted, and m is an integer between 3 and103, such that n is less than or equal to (m−2). In some embodiments, nis an integer between 1 and 5. In some embodiments, m is an integerbetween 3 and 7. Some specific examples of brightening agents include,but are not limited to, propargyl-oxo-propane-2,3-dihydroxy (POPDH) andpropargyl-3-sulfopropyl ether Na salt (POPS). It should be understoodthat other alkynyl alkoxy alkanes may also be useful as brighteningagents.

In some cases, the brightening agent may comprise an alkyne. Forexample, the alkyne may be a hydroxy alkyne. In some embodiments, thebrightening agent may comprise a compound having the following formula,[R³]_(x)—C≡C—[R⁴]_(y),wherein R³ and R⁴ can be the same or different and each is H, alkyl,hydroxyalkyl, or amino optionally substituted, and x and y can the besame or different and each is an integer between 1 and 100. In somecases, at least one of R³ or R⁴ comprises a hydroxyalkyl group. In someinstances, at least one of R³ or R⁴ comprises an amino functional group.In some embodiments, x and y can be the same or different and areintegers between 1-5, and at least one of R³ and R⁴ comprises ahydroxyalkyl group. In an illustrative embodiment, the alkyne is2-butyne-1,4-diol. In another illustrative embodiment, the alkyne is1-diethylamino-2-propyne. It should be understood that other alkynes mayalso be useful as brightening agents within the context of theinvention.

In some cases, the brightening agent may be chosen from those moleculesfalling within the betain family, where a betain is a neutrally chargedcompound comprised of a positively charged cationic functional group anda negatively charged anionic functional group. Here examples of thecationic side of the betain could be ammonium, phosphonium, orpyridinium groups optionally substituted, and examples of the anionicside could be carboxylic, sulfonic, or sulfate groups. It should beunderstood that these functional groups are for illustration and are notintended to be limiting.

In some cases, the electrodeposition baths may include a combination ofat least two brightening agents. For example, a bath may comprise both abrightening agent comprising an alkynyl alkoxy alkane and a secondbrightening agent comprising an alkyne.

The baths may comprise the brightening agent in a concentration of from0.05 g/L to 5 g/L, from 0.05 g/L to 3 g/L, from 0.05 g/L to 1 g/L, or,in some cases, from 0.01 g/L to 1 g/L. In some cases, the baths maycomprise the brightening agent in a concentration of from 0.05 g/L to 1g/L, from 0.05 g/L to 0.50 g/L, from 0.05 g/L to 0.25 g/L, or, in somecases, from 0.05 g/L to 0.15 g/L. Those of ordinary skill in the artwould be able to select the concentration of brightening agent, ormixture of brightening agents, suitable for use in a particularapplication.

Those of ordinary skill in the art would be able to select theappropriate brightening agent, or combination of brightening agents,suitable for use in a particular invention. In some embodiments, thealkynyl alkoxy alkane, alkyne, or other brightening agent may beselected to exhibit compatibility (e.g., solubility) with theelectroplating bath and components thereof. For example, the brighteningagent may be selected to include one or more hydrophilic species toprovide greater hydrophilicity to the brightening agent. The hydrophilicspecies can be, for example, amines, thiols, alcohols, carboxylic acidsand carboxylates, sulfates, phosphates, polyethylene glycols (PEGs), orderivatives of polyethylene glycol. The presence of a hydrophilicspecies can impart enhanced water solubility to the brightening agent.For example, R¹, R², and/or R³ as described above may be selected tocomprise a hydroxyl group or a sulfate group.

In some cases, the baths may include at least one wetting agent. Awetting agent refers to any species capable of increasing the wettingability of the electrodeposition bath with the surface of the article tobe coated. For example, the substrate may comprise a hydrophilicsurface, and the wetting agent may enhance the compatibility (e.g.,wettability) of the bath relative to the substrate. In some cases, thewetting agent may also reduce the number of defects within the metalcoating that is produced. The wetting agent may comprise an organicspecies, an inorganic species, an organometallic species, orcombinations thereof. In some embodiments, the wetting agent may beselected to exhibit compatibility (e.g., solubility) with theelectroplating bath and components thereof. For example, the wettingagent may be selected to include one or more hydrophilic species,including amines, thiols, alcohols, carboxylic acids and carboxylates,sulfates, phosphates, polyethylene glycols (PEGs), or derivatives ofpolyethylene glycol, to enhance the water solubility of the wettingagent.

In one set of embodiments, the wetting agent may comprise an aromaticgroup, optionally substituted. For example, the wetting agent maycomprise a naphthyl group substituted with one or more an alkyl orheteroalkyl group, optionally substituted.

In some cases, the wetting agent may comprise a sulfopropylatedpolyalkoxy napthol having the following formula,

wherein R⁵ comprises an alkyl or heteroalkyl group. In some cases, R⁵comprises a charged group, such as SO₃. For example, the wetting agentmay comprise the group, —(CH₂)₃SO₃. In some embodiments, R⁵ may comprisea group having the formula (R⁶)_(q), wherein R⁶ is alkyl or heteroalkyl,optionally substituted, and q is an integer between 1-100. In anillustrative embodiment, the wetting agent may be Ralufon NAPE 14-90(Raschig GmbH).

In another set of embodiments, the wetting agent may comprise afluorocarbon, optionally substituted. The fluorocarbon could be fully orpartially fluorinated. The wetting agent could be chosen from the groupsof anionic, non-ionic and amphoteric fluorocarbons. For example, ananionic wetting agent may comprise a fluorocarbon substituted with ananionic moiety such as a carboxylate, sulfonate, sulfate, phosphate,etc. An example of an anionic fluorinated wetting agent is C₈F₁₇SO₃Na.Non-ionic wetting agents are substantially non-dissociated in anelectroplating bath, for example C₈F₁₇—CH₂—CH₂—O—(CH₂—CH₂—O)_(n)—H.Amphoteric wetting agents have at least one anionic and cationic moiety.An example of an amphoteric fluorinated wetting agent isC₆F₁₃—(CH₂)₂—SO₂—HN—(CH₂)₃—N(CH₃)₂—CH₂—COOH.

Additives described herein can be used both individually and/or in anycombinations thereof to provide improved coating quality throughbrightening, leveling and reduction in propensity for surface pitting.

In some embodiments, the electrodeposition bath may include additionaladditives. For example, the electrodeposition bath may comprise one ormore complexing agents. A complexing agent refers to any species whichcan coordinate with the metallic ions contained in the solution. Thecomplexing agent may be an organic species, such as a citrate ion, or aninorganic species, such as an ammonium ion. In some cases, thecomplexing agent is a neutral species. In some cases, the complexingagent is a charged species (e.g., negatively charged ion, positivelycharged ion). Examples of complexing agents include citrates,gluconates, tartrates, and other alkyl hydroxyl carboxylic acids.Generally, a complexing agent, or mixture of complexing agents, may beincluded in the electrodeposition bath within a concentration range of10-200 g/L, and, in some cases, within the range of 40-80 g/L. In oneembodiment, the complexing agent is a citrate ion. In some embodiments,ammonium ions may be incorporated into the electrolyte bath ascomplexing agents and to adjust solution pH. For example, theelectrodeposition bath may comprise ammonium ions in the range of 1-50g/L, and between 10-30 g/L.

Those of ordinary skill in the art would be able to select theappropriate combination of brightening agent, wetting agent, and/orother additives suitable for use in a particular application. Forexample, a screening test for selection of a bath component may includeelectroplating a coating using a particular bath composition asdescribed herein, or series of bath compositions, and comparing theresulting coating(s) formed to determine the bath composition thatproduces the desired coating or coating characteristic. In one set ofembodiments, a series of bath compositions, each including a differentbrightening agent, may be used to electroplate a series of coatings. Thecharacteristics (e.g., appearance, stability, etc.) of the resultingcoatings may then be evaluated to select the appropriate brighteningagent. Similar screening tests may also be employed for other bathcomponents, including wetting agent and/or other additives.

As used herein, the term “alkyl” refers to the radical of saturatedaliphatic groups, including straight-chain alkyl groups, branched-chainalkyl groups, cycloalkyl (alicyclic) groups, alkyl substitutedcycloalkyl groups, and cycloalkyl substituted alkyl groups. The alkylgroups may be optionally substituted, as described more fully below.Examples of alkyl groups include, but are not limited to, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.“Heteroalkyl” groups are alkyl groups wherein at least one atom is aheteroatom (e.g., oxygen, sulfur, nitrogen, phosphorus, etc.), with theremainder of the atoms being carbon atoms. Examples of heteroalkylgroups include, but are not limited to, alkoxy, poly(ethylene glycol)-,alkyl-substituted amino, tetrahydrofuranyl, piperidinyl, morpholinyl,etc.

The terms “alkenyl” and “alkynyl” refer to unsaturated aliphatic groupsanalogous to the alkyl groups described above, but containing at leastone double or triple bond respectively. The “heteroalkenyl” and“heteroalkynyl” refer to alkenyl and alkynyl groups as described hereinin which one or more atoms is a heteroatom (e.g., oxygen, nitrogen,sulfur, and the like).

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds, “permissible” being inthe context of the chemical rules of valence known to those of ordinaryskill in the art. In some cases, “substituted” may generally refer toreplacement of a hydrogen with a substituent as described herein.However, “substituted,” as used herein, does not encompass replacementand/or alteration of a key functional group by which a molecule isidentified, e.g., such that the “substituted” functional group becomes,through substitution, a different functional group. For example, a“substituted heteroalkyl” must still comprise the heteroalkyl moiety andcan not be modified by substitution, in this definition, to become,e.g., an alkyl group. In a broad aspect, the permissible substituentsinclude acyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, thosedescribed herein. The permissible substituents can be one or more andthe same or different for appropriate organic compounds. For purposes ofthis invention, the heteroatoms such as nitrogen may have hydrogensubstituents and/or any permissible substituents of organic compoundsdescribed herein which satisfy the valencies of the heteroatoms. Thisinvention is not intended to be limited in any manner by the permissiblesubstituents of organic compounds.

Examples of substituents include, but are not limited to, alkyl, aryl,aralkyl, cyclic alkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy,perhaloalkoxy, aralkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl,heteroaralkoxy, azido, amino, halogen, alkylthio, oxo, acylalkyl,carboxy esters, carboxyl, -carboxamido, nitro, acyloxy, aminoalkyl,alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino,aralkylamino, alkylsulfonyl, carboxamidoalkylaryl, carboxamidoaryl,hydroxyalkyl, halo alkyl, alkylaminoalkylcarboxy, aminocarboxamidoalkyl,alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl, and the like.

In some aspects, various techniques can be used to monitor the contentsof the electrodeposition baths. For example, the techniques maydetermine the concentration of one or more of the additives in the bathsuch as the brightening agent(s), wetting agent(s), complexing agent(s),etc. If the concentration of the additive(s) is below or above a desiredconcentration, the bath composition may be adjusted so that theconcentration lies within the desired range.

In some embodiments, techniques for determining the concentration of abrightening agent comprising an alkyne (e.g. a hydroxy alkyne) compound,are provided. In some cases, the compound may be a diol, such a2-butyne-1,4-diol. The techniques generally involve removing a samplefrom the electroplating bath. In some instances, an oxidizing agent isreacted with the alkyne to produce a reacted alkyne. As described below,the reacted alkyne may be analyzed. In some methods, the alkyne isextracted from a sample taken from the electrodeposition bath using asolvent (e.g., an organic solvent, such as butyl acetate). The solventcontaining the alkyne, in some cases, is treated with an aqueoussolution containing an oxidizing agent (e.g. potassium permanganate, achromium compound, etc.) to produce a reacted alkyne and adistinguishable color change. In some instances, using colorimetry, thesolution having a distinguishable color can be compared to a set ofcolored solutions generated using a known quantity of alkyne todetermine the concentration of alkyne in the electrodeposition bath. Bydetermining the concentration of alkyne in the electrodeposition bath,adjustments can be made to the electrodeposition bath to produce adesired concentration of alkyne.

In other embodiments, the invention provides techniques for determiningthe concentration of a brightening agent comprising an alkynyl alkoxyalkane compound. In some embodiments, the alkynyl alkoxy alkane compoundcan be a terminal alkyne, such as POPS and/or POPDH. The techniquesgenerally involve removing a sample from the electroplating bath. Insome methods, a metal compound is added to the sample which reacts withthe alkynyl alkoxy alkane compound to form a metal-bound species. Asdescribed further below, the metal-bound species may be analyzed. Insome methods, the pH of the sample is adjusted to a value above pH 7(e.g., about pH 8) by the addition of an alkaline solution (e.g.,aqueous sodium hydroxide) prior to adding the metal compound. In somemethods, the alkynyl alkoxy alkane can be precipitated when the metalcompound is added to form the metal-bound species, which may be in theform of a suspension of particles in solution. Some examples of suitablemetal compounds for precipitation of the alkynyl alkoxy alkane aresilver compounds (e.g. silver nitrate) and/or copper compounds [e.g.copper(I) chloride]. The turbidity of the metal-bound species, which maybe in the form of a suspension of particles, can be measured using, forexample, a turbidity meter. A standard curve for alkynyl alkoxy alkaneconcentration versus turbidity can be generated, for example, using theturbidity values of a set of solutions containing a range of knownconcentrations of the alkynyl alkoxy alkane and plotting the turbidityvalues against the known concentrations of the alkynyl alkoxy alkane.Fitting a curve to the resultant plot, using a method such as a linearregression, can allow the derivation of a general mathematical formulafor calculating the concentration of the alkynyl alkoxy alkane in asample having an unknown concentration of the alkynyl alkoxy alkane byinputting the turbidity value of the sample into the formula.

In other instances, potentiometry can be used to analyze the metal-boundspecies. In some methods, the amount of unreacted metal compound in thesample is determined by potentiometric titration and is used tocalculate the amount of metal-bound species formed by the reaction ofthe metal compound with the alkynyl alkoxy alkane. In some embodiments,a thiocyanate (e.g. potassium thiocyanate) solution is used to titratethe sample containing the unreacted metal compound and determine theamount of metal compound remaining after reaction of the metal compoundwith the alkynyl alkoxy alkane. Generally, the amount of metal-boundspecies formed by reaction of the metal compound with the alkynyl alkoxyalkane is proportional to the amount of the metal compound consumedduring the reaction and can be calculated by subtracting the amount ofmetal compound remaining after reaction of the metal compound with thealkynyl alkoxy alkane from the initial amount of metal compound added tothe sample. As described above for analyzing the metal-bound species bymeasuring turbidity, an analogous standard curve for alkynyl alkoxyalkane concentration versus amount of titrant consumed can be generated,thereby allowing a mathematical formula for calculating theconcentration of the alkynyl alkoxy alkane in a sample having an unknownconcentration of the alkynyl alkoxy alkane to be derived. By determiningthe concentration of alkynyl alkoxy alkane in the electrodepositionbath, adjustments can be made to the electrodeposition bath to produce adesired concentration of alkynyl alkoxy alkane.

In additional embodiments, a method is provided for determining theconcentration of a wetting agent. In some instances, the wetting agentcomprises a sulfopropylated polyalkoxy napthol such as Ralufon NAPE14-90. An electrodeposition bath sample can be combined with a solvent(e.g. chloroform) and an indicator solution. In one example, theindicator solution comprises two indicator dyes such as dimidium bromideand patent blue. The mixture containing the sample, solvent, andindicator solution can be titrated with a titrating agent until adistinguishable color change can be observed. In some instances, thesolvent in the mixture is pink in color, and benzethonium chloride (atitrating agent) is added to the mixture until the solvent is blue incolor. A standard curve for wetting agent concentration versus amount ofbenzethonium chloride titrated can be generated, for example, using theamount of benzethonium chloride titrated in a set of solutionscontaining a range of known concentrations of the wetting agent andplotting the amount of benzethonium chloride titrated against the knownconcentrations of the wetting agent. Fitting a curve to the resultantplot, using a method such as a linear regression, can allow thederivation of a general mathematical formula for calculating theconcentration of the wetting agent in a sample having an unknownconcentration of the wetting agent by inputting the amount ofbenzethonium chloride titrated in the mixture of sample, solvent, andindicator solution into the formula. By determining the concentration ofwetting agent in the electrodeposition bath, adjustments can be made tothe electrodeposition bath to produce a desired concentration of wettingagent.

In general, the electrodeposition baths can be used in connection withany electrodeposition process. Electrodeposition generally involves thedeposition of a coating on a substrate by contacting the substrate withan electrodeposition bath and flowing electrical current between twoelectrodes through the electrodeposition bath, i.e., due to a differencein electrical potential between the two electrodes. For example, methodsdescribed herein may involve providing an anode, a cathode, anelectrodeposition bath associated with (e.g., in contact with) the anodeand cathode, and a power supply connected to the anode and cathode. Insome cases, the power supply may be driven to generate a waveform forproducing a coating, as described more fully below. In some embodiments,at least one electrode may serve as the substrate to be coated.

The electrodeposition may be modulated by varying the potential that isapplied between the electrodes (e.g., potential control or voltagecontrol), or by varying the current or current density that is allowedto flow (e.g., current or current density control). In some embodiments,the coating may be formed (e.g., electrodeposited) using direct current(DC) plating, pulsed current plating, reverse pulse current plating, orcombinations thereof. Pulses, oscillations, and/or other variations involtage, potential, current, and/or current density, may also beincorporated during the electrodeposition process, as described morefully below. For example, pulses of controlled voltage may be alternatedwith pulses of controlled current or current density. In general, duringan electrodeposition process an electrical potential may exist on thesubstrate to be coated, and changes in applied voltage, current, orcurrent density may result in changes to the electrical potential on thesubstrate. In some cases, the electrodeposition process may include theuse of waveforms comprising one or more segments, wherein each segmentinvolves a particular set of electrodeposition conditions (e.g., currentdensity, current duration, electrodeposition bath temperature, etc.), asdescribed more fully below.

In some embodiments, a coating, or portion thereof, may beelectrodeposited using direct current (DC) plating. For example, asubstrate (e.g., electrode) may be positioned in contact with (e.g.,immersed within) a electrodeposition bath comprising one or more speciesto be deposited on the substrate. A constant, steady electrical currentmay be passed through the electrodeposition bath to produce a coating,or portion thereof, on the substrate.

In some cases, the electrodeposition method involves driving a powersupply to generate a waveform to electrodeposit a coating. The waveformmay have any shape, including square waveforms, non-square waveforms ofarbitrary shape, and the like. As described further below, in somemethods such as when forming coatings having different portions, thewaveform may have different segments used to form the differentportions. However, it should be understood that not all methods usewaveforms having different segments.

In some cases, a bipolar waveform may be used, comprising at least oneforward pulse and at least one reverse pulse, i.e., a “reverse pulsesequence.” As noted above, the electrodeposition baths described hereinare particularly well suited for depositing coatings using complexwaveforms such as reverse pulse sequences. In some embodiments, the atleast one reverse pulse immediately follows the at least one forwardpulse. In some embodiments, the at least one forward pulse immediatelyfollows the at least one reverse pulse. In some cases, the bipolarwaveform includes multiple forward pulses and reverse pulses. Someembodiments may include a bipolar waveform comprising multiple forwardpulses and reverse pulses, each pulse having a specific current densityand duration. In some cases, the use of a reverse pulse sequence mayallow for modulation of composition and/or grain size of the coatingthat is produced.

In some embodiments, a reverse pulse sequence may be applied such thatthe forward (e.g., positive) current density, when integrated over theduration of the forward current pulse(s), is of a similar magnitude tothe reverse (e.g., negative) current density integrated over theduration of the reverse current segment. FIG. 2 shows an example of areverse pulse sequence, wherein portions A represent the reverse currentdensity integrated over the duration of the reverse current pulse(s) andportions B represent the forward current density integrated over theduration of the forward current pulse(s).

As noted above, some embodiments may include a waveform having more thanone segment, each segment including a particular set ofelectrodeposition conditions. That is, the waveform is different indifferent segments. For example, the waveform may include one segmentcomprising at least one forward pulse and at least one reverse pulse(e.g., a bipolar waveform or a reverse pulse sequence), and anothersegment comprising a single forward, or reverse, pulse. In some cases,the segment having the single pulse may be arranged prior to the segmenthaving the reverse pulse sequence. For example, FIG. 3 shows an exampleof a waveform comprising (i) a first segment including a single, forwardpulse and (ii) a second segment including a reverse pulse sequence,according to one embodiment of the invention. In some cases, the secondsegment is similar to the waveform shown in FIG. 2. It also should beunderstood that the waveform may have more segments in addition to thefirst and second segments.

The methods of the invention may utilize certain aspects of methodsdescribed in U.S. Patent Publication No. 2006/02722949, entitled “Methodfor Producing Alloy Deposits and Controlling the Nanostructure Thereofusing Negative Current Pulsing Electro-deposition, and ArticlesIncorporating Such Deposits,” which is incorporated herein by referencein its entirety. Aspects of other electrodeposition methods may also besuitable including those described in U.S. Patent Publication No.2006/0154084 and U.S. application Ser. No. 11/985,569, entitled “Methodsfor Tailoring the Surface Topography of a Nanocrystalline or AmorphousMetal or Alloy and Articles Formed by Such Methods”, filed Nov. 15,2007, and U.S. patent application Ser. No. 12/120,564, filed May 14,2008 which are incorporated herein by reference in their entireties.

The coating comprises one or more metals. For example, the coating maycomprise an alloy (e.g., a nickel-tungsten alloy). Examples of suitablealloys may include two or more of the following elements: Ni, W, Fe, B,S, Co, Mo, Cu, Cr, Zn and Sn, amongst others. In some cases, alloys thatcomprises tungsten (e.g., nickel-tungsten alloys) are particularlypreferred. Some specific examples of alloys include Ni—W, Ni—Fe—W,Ni—B—W, Ni—S—W, Co—W, Ni—Mo, Co—Mo and Ni—Co—W.

In some cases, the coating may be combined with additional phases. Forexample, hard particulates of metal, ceramic, intermetallic, or othermaterial might be incorporated into the coating. Other potential phaseswhich may be incorporated will also be recognized by those skilled inthe art, such as solid lubricant particles of graphite or MoS₂.

In some embodiments, it may be advantageous for the coating to besubstantially free of elements or compounds having a high toxicity orother disadvantages. In some embodiments, it may be advantageous for thecoating to be substantially free of elements or compounds that aredeposited using species that have a high toxicity or otherdisadvantages. For example, in some cases, the coating may be free ofchromium (e.g., chromium oxide) since it is often deposited usingchromium ionic species (e.g., Cr⁶⁺) which are toxic. Such coatings mayprovide various processing, health, and environmental advantages overprevious coatings.

The coating may have any thickness suitable for a particularapplication. For example, the total coating thickness may be between 10nm and 1 mm; in some cases, between 100 nm and 200 micron; and, in somecases, between 100 nm and 100 micron.

It should be understood, however, that the coating may also have otherthicknesses outside the above-noted ranges.

In some cases, the coatings may have a particular microstructure. Forexample, at least a portion of the coating may have a nanocrystallinemicrostructure. As used herein, a “nanocrystalline” structure refers toa structure in which the number-average size of crystalline grains isless than one micron. The number-average size of the crystalline grainsprovides equal statistical weight to each grain and is calculated as thesum of all spherical equivalent grain diameters divided by the totalnumber of grains in a representative volume of the body. In someembodiments, at least a portion of the coating may have an amorphousstructure. As known in the art, an amorphous structure is anon-crystalline structure characterized by having no long range symmetryin the atomic positions. Examples of amorphous structures include glass,or glass-like structures. Some embodiments may provide coatings having ananocrystalline structure throughout essentially the entire coating.Some embodiments may provide coatings having an amorphous structurethroughout essentially the entire coating.

Various substrates may be coated to form coated articles, as describedherein. In some cases, the substrate may comprise an electricallyconductive material, such as a metal, metal alloy, intermetallicmaterial, or the like. Suitable substrates include steel, copper,aluminum, brass, bronze, nickel, polymers with conductive surfacesand/or surface treatments, transparent conductive oxides, amongstothers.

The following examples are provided for illustration purposes and arenot intended to be limiting.

EXAMPLES

Several experiments were conducted to illustrate some embodiments of thepresent inventions. The experiments involved coatings of Ni—W alloysproduced by aqueous electrodeposition.

Example 1

This example demonstrates the use of alkynyl alkoxy alkanes, asbrightening agents in the deposition of Ni—W alloy coatings. Brushedsteel articles were coated with Ni—W alloys by electrodeposition from anaqueous electrodeposition bath. Each article was immersed in anelectrodeposition bath, and a DC current was applied using stainlesssteel counter electrodes. A 267 mL Hull Cell operating at 3 amperes and60° C. for 10 minutes with air agitation of the electrodeposition bathwas used to produce the coated articles. Coated articles formed usingthis method provided a current density evaluation range of about 0amperes per square foot (ASF) to 225 ASF. Articles were chemicallyprepared prior to plating as is well known in the art.

TABLE 1 Solution A composition. Nickel metal (from nickel sulfate) 6.5g/L Tungsten metal (from sodium tungstate) 32.5 g/L Citric acid 64 g/LAmmonium hydroxide to pH ~8.0 ~20 g/L Sufficient water to produce 1 L ofsolution

Solution A was used as the basic electrolyte solution for theelectrodeposition baths demonstrated in this example, and brighteningagents from the family of alkynyl alkoxy alkanes were added to thissolution in concentrations from 0 to ˜0.5 g/L. A hull cell test panelwas prepared as described above from Solution A with no additives, andthe resulting Ni—W alloy coating produced from this solution wasmatte/semi-bright below a current density of 20 ASF and hazy/mattegreater than a current density of 20 ASF. Article 1A served as thereference sample for comparison to articles coated usingelectrodeposition baths containing additives.

Articles 1B-F were produced from electrodeposition baths containingSolution A and alkynyl alkoxy alkane additives at concentrations rangingfrom ˜0.05 to ˜0.5 g/L. The surface finishes of the coated articlesvaried as a function of the additive concentration and the currentdensity, and each coated article in this example produced usingelectrodeposition baths containing an additive demonstrated improvedbrightening/leveling in the deposited coating as compared to thereference sample (Article 1A). Here bright coatings were produced acrossa 200 ASF current density range. Increases in concentration producedbrighter coatings at higher current densities than lower concentrations.

Example 2

This example demonstrates the use of hydroxy alkynes as brighteningagents in the deposition of Ni—W alloy coatings. Articles in thisexample were produced in the same fashion as those in Example 1described above.

Article 1A from Example 1 served as a reference for this example. Asdescribed above, the resulting Ni—W alloy coating produced from thissolution was matte/semi-bright at a current density below 20 ASF andhazy/matte at a current density greater than 20 ASF.

Solution A from Example 1 was used as the basic electrolyte solution forthe electrodeposition baths demonstrated in this example, andbrightening agents were added to this solution in concentrations from˜0.02 to ˜0.1 g/L.

Articles 2B-D were produced from electrodeposition baths containingSolution A and a hydroxy alkyne additive at concentrations ranging from˜0.02 g/L to ˜0.1 g/L. The surface finish of the coated articles variedas a function of the additive concentration and the current density, andeach coated article in Example 2 produced using electrodeposition bathscontaining an additive demonstrated improved brightening/leveling in thedeposited coating as compared to the reference sample (Article 1A).Increases in concentration increased the brightness of the coatings atlow to medium current densities.

Example 3

This example demonstrates the use of betains as brightening agents inthe deposition of Ni—W alloy coatings. Articles in this example wereproduced in the same fashion as those in Example 1 described above.

Article 1A from Example 1 served as a reference for this example. Asdescribed above, the resulting Ni—W alloy coating produced from thissolution was matte/semi-bright at a current density below 20 ASF andhazy/matte at a current density greater than 20 ASF.

Solution A from Example 1 was used as the basic electrolyte solution forthe electrodeposition baths demonstrated in this example, andbrightening agents were added to this solution in concentrations from˜0.1 to ˜10 g/L.

Articles 3B-E were produced from electrodeposition baths containingSolution A and a betain additive at concentrations ranging from ˜0.1 g/Lto ˜10 g/L. The surface finish of the coated articles varied as afunction of the additive concentration and the current density, and eachcoated article in Example 3 produced using electrodeposition bathscontaining an additive demonstrated improved brightening/leveling in thedeposited coating as compared to the reference sample (Article 1A).Increases in concentration increased the brightness of the coatings atlow to medium current densities.

Example 4

This example demonstrates the use of polyalkoxylated naphthols aswetting agents in the deposition of Ni—W alloy coatings. Articles inthis example were produced in the same fashion as those in Example 1described above.

Article 1A from Example 1 served as a reference for this example. Asdescribed above, the resulting Ni—W alloy coating produced from thissolution was matte/semi-bright at a current density below 20 ASF andhazy/matte at a current density greater than 20 ASF.

Solution A from Example 1 was used as the basic electrolyte solution forthe electrodeposition baths demonstrated in this example, and wettingagents were added to this solution in concentrations from 0.1-1 g/L.

Articles 4B-F were produced from electrodeposition baths containingSolution A and wetting agents chosen from the polyalkoxylated naphtholand anionic fluorocarbon families at concentrations of 0.1-1.0 g/L. Asmall degree of brightening was observed at all concentrations ofwetting agents relative to the reference (Article 1A). Coatingconditions shown to produce pitting in the deposit with Solution A wereevaluated using the wetting agents in conjunction with Solution A.Incorporation of the wetting agents demonstrated reduced, and in somecases completely eliminated, pitting defects from the coatings.

Example 5

This example demonstrates the combined use of two brightening agents inthe deposition of Ni—W alloy coatings. Articles in this example wereproduced in the same fashion as those in Example 1 described above.

Article 1A from Example 1 served as a reference for this example. Asdescribed above, the resulting Ni—W alloy coating produced from thissolution was matte/semi-bright at a current density below 20 ASF andhazy/matte at a current density greater than 20 ASF.

Solution A from Example 1 was used as the basic electrolyte solution forthe electrodeposition baths demonstrated in this example, andcombinations of the brightening agents used in Examples 1(0.12, 0.5g/L), 2(0.05 g/L), and 3(2 g/L) were added.

Articles 5B-E were produced from electrodeposition baths containingSolution A and combinations of the alkynyl alkoxy alkane, hydroxyalkyne, and betain additives. Complementary brightening/leveling wasobserved on coated articles in all examples, and each article in Example5 produced using electrodeposition baths containing a combination ofadditives demonstrated improved brightening/leveling in the depositedcoating as compared to the reference sample (Article 1A) and coatedarticles produced using electrodeposition baths containing only onebrightening agent, as described in Examples 1, 2, and 3.

Example 6

This example demonstrates the combined use of a brightening agent and awetting agent in the deposition of Ni—W alloy coatings. Articles in thisexample were produced in the same fashion as those in Example 1described above.

Article 1A from Example 1 served as a reference for this example. Asdescribed above, the resulting Ni—W alloy coating produced from thissolution was matte/semi-bright at a current density below 20 ASF andhazy/matte at a current density greater than 20 ASF.

Solution A from Example 1 was used as the basic electrolyte solution forthe electrodeposition baths demonstrated in this example, andbrightening (Example 1: 0.12 g/L, 0.24 g/L) and wetting (Example 4: 0.4g/L) agents were added.

Articles 6B-C were produced from electrodeposition baths containingSolution A and the combination of a alkynyl alkoxy alkane andpolyalkoxylated naphthol additives. Complementary coating quality, asevidenced by reduced propensity to surface pitting, was observed oncoated articles produced from both electrodeposition baths as comparedto coated articles produced using electrodeposition baths containingonly one brightening agent, as shown in Examples 1 and 4. Each articlein Example 6 demonstrated improved brightening/leveling in the depositedcoating as compared to the reference sample (Article 1A).

Example 7

This example demonstrates the combined use of two brightening agents anda wetting agent in Ni—W alloy coatings. Articles in this example wereproduced in the same fashion as those in Example 1 described above.

Article 1A from Example 1 served as a reference for this example. Asdescribed above, the resulting Ni—W alloy coating produced from thissolution was matte/semi-bright at a current density below 20 ASF andhazy/matte at a current density greater than 20 ASF.

Solution A from Example 1 was used as the basic electrolyte solution forthe electrodeposition baths demonstrated in this example, andbrightening agents (Example 1: 0.12 g/L, 0.24 g/L, 0.48 g/L; Example 2:0.075 g/L) and a wetting agent (Example 4: 0.4 g/L) were added.

Articles 7B-D were produced from electrodeposition baths containingSolution A and combinations of a alkynyl alkoxy alkane, a hydroxyalkyne, and a polyalkoxylated naphthol. Complementarybrightening/leveling and reduced propensity to surface pitting wereobserved on coated articles produced using each electrodeposition bathas compared to coated articles produced using electrodeposition bathscontaining only one brightening or wetting agent, as described inExamples 1, 2, 4, and as compared to coated articles produced usingelectrodeposition baths containing two additives, as described inExamples 5 and 6. Each article in Example 7 demonstrated improvedbrightening/leveling in the deposited coating as compared the referencesample (Article 1A).

Having thus described several aspects of at least one embodiment of thisinvention, it is to be appreciated various alterations, modifications,and improvements will readily occur to those skilled in the art. Suchalterations, modifications, and improvements are intended to be part ofthis disclosure, and are intended to be within the spirit and scope ofthe invention. Accordingly, the foregoing description and drawings areby way of example only.

1. A method for analyzing an alkyne compound in an electroplating bath,comprising: removing a sample from an electroplating bath comprising atungsten and/or molybdenum ionic species, an ionic species of a secondmetal, a brightening agent comprising an alkynyl alkoxy alkane compound,and a secondary brightening agent comprising a alkyne compound;extracting the alkyne compound from the sample by addition of an organicsolvent to the sample; reacting the alkyne with an oxidizing agent toproduce a reacted alkyne; and analyzing the reacted alkyne.
 2. Themethod of claim 1, wherein the organic solvent comprises butyl acetate.3. The method of claim 1, wherein the oxidizing agent comprisespermanganate.
 4. The method of claim 1, wherein the oxidizing agentcomprises a chromium compound.
 5. The method of claim 1, whereinanalyzing the reacted alkyne comprises colorimetry.
 6. The method ofclaim 1, wherein the second metal is nickel.
 7. The method of claim 1,wherein the alkyne comprises a hydroxy alkyne.
 8. The method of claim 7,wherein the hydroxy alkyne is 2-butyne-1,4-diol.